Microbiocidal polymeric quarternary ammonium compounds

ABSTRACT

The use of polymeric quaternary ammonium compounds prepared by the condensation of 1,4-dihalo-2-butene and 1,4-bisdimethylamino-2-butene as microbiocidal agents in aqueous systems.

United States Patent [11] 3,874,870 Green et al. Apr. 1, 1975MICROBIOCIDAL POLYMERIC [56] References Cited QUARTERNARY AMMONIUMUNITED STATES PATENTS COMPOUNDS 3,140,976 7/1964 Berenschot et a1.424/329 [75] Inventors; Harold A, Green, Havertown P3; 3,539,684 11/1970Hoover 424/78 J Mel-ianos Jersey Ci 3,771,989 11/1973 Pera et al 424/329Alfonso N. Petrocci, Glen Rock7 3,778,283 12/1973 Freyhold 106/84 bothof FOREIGN PATENTS OR APPLICATIONS [73] Assignee: Mill Master OnyxCorporation, New 69-8949 7/1970 South rica York, N.Y.

Primary Examiner-Albert T. Meyers [22] Flled' 1973 AssistantExaminer-Douglas W. Robinson [21] App]. No.: 425,931 Attorney, Agent, orFirmArthur A. Jacobs, Esq.

52 U.S. Cl 71/67, 260/875 R, 424/78, ABSTRACT 424/329 The use ofpolymeric quaternary ammonium com- 1 AOIN AOlN A61K 0 pounds prepared bythe condensation of 1,4-diha1o-2- A61K 17/00 butene andl,4-bis-dimethylamino-Z-butene as micro- Fleld of Search biocidal agentsin aqueQuS Systems,

8 Claims, N0 Drawings MlCROBIOClDAL POLYMERIC QUARTERNARY AMMONIUMCOMPOUNDS This invention relates to microbiocidal agents, and itparticularly relates to microbiocidal agents comprising polymericquaternary ammonium compounds.

It is known that many quaternary ammonium compounds have biocidal orinhibitory effects on microorganisms. However, few such compounds, orindeed few biocidal compounds of any type, have been found to have allthe necessary characteristics required for the biocidal treatment ofaqueous systems of the recirculated type such as industrial or processwaters of the type used in paper manufacturing, cooling towers, airconditioners, humidifiers and the like. Even relatively standing waterssuch as swimming pools have been problems insofar as maintaining themsubstantially free of bacteria, fungi and algae,

The control of microorganisms in aqueous systems of the aforesaid typehas long been recognized as a particularly burdensome problem since theenvironment of the aqueous medium itselfis often extremely conducive torapid multiplication and growth of these undesirable organisms. Onlythrough the rise of carefully tailored microbiocidal agents can thisgrowth and reproduction be reliably controlled without detriment to theprocess in which the water is used. For example, many times a n X-CHbiocidal compound is rendered completely inactive by the particularsurrounding media containing the undesirable microorganisms. Aparticular problem in recirculated waters is that the recirculationcauses many difficult problems, among which is the gradual build-up andaccumulation of undesirable microorganisms in the aqueous fluid. Variousbacteria, fungi and algae are favorably produced in such recirculatedwaters.

Another common feature of quaternary ammonium biocides is that theirbiocidal effectiveness is diminished in the presence of non-ionicemulsifiers, often to the point where they no longer function asacceptable biocides. This has significantly reduced their possible usein cosmetics and similar preparations that require the inclusion ofnon-ionic emulsifiers.

An additional problem in the use of most microbiocidal agents in aqueoussystems is the formation of large amounts of foam. This foam isgenerally highly undesirable and the formation thereof by these agentsoften makes them useless for particular applications.

In accordance with the present invention, it has now been discoveredthat certain polymeric quaternary ammonium compounds and, particularly,the product made by the condensation of 1,4-dihalo-2-butene andl,4-bis-dimethylamino-2-butene is not only a highly effectivemicrobiocidal agent in aqueous systems, including recirculating waters,industrial waters, cosmetics and other emulsions containing non-ionicemulsifiers, as well as in general usage, but also effects such purposewithout causing undue foaming.

It is to be noted that a particular aspect of the present invention isthat the quaternary ammonium moieties of -CH=CH-CH X n (CH the presentcompounds are part of a long chain rather than being on branches thatare bonded to the long chain.

The aforesaid compounds are active against Pseudomonas aeruginosa at aconcentration relative to the total composition as low as 25 ppm,although the preferred concentration is about 150 ppm. AgainstAerohacter acrogenes, they are active at a concentration as low as ppm,although the preferred concentration is about 100 ppm. Against algae,such as Chlorella pyrenoidosa, they are active at a concentration atleast as low as 1 ppm and probably even much below that concentrationaccording to present indications.

Insofar as concerns upper limits, the concentration may apparently beincreased indefinitely without deleteriously affecting the biocidalactivity.

More specifically with regard to cosmetic compositions. the products ofthis invention are effective at a concentration at least as low as about500 ppm relative to the total composition, and probably at even lowerconcentrations, according to present indications. The preferred range,however, is about I ,000 to 2,000 ppm.

There is no absolute certainty of the actual structure of the product ofthe condensation reaction because isomerizations are possible. However,ideally, the reaction would appear to be as follows:

wherein X is a halogen such as chlorine or bromine and n is an integerfrom about 2 to 30.

The following examples illustrate the present invention with no intentto be limited thereby, however, except as claimed:

EXAMPLE 1 14.2 grams of l,4-bis-dimethylamino-Z-butene (0.1 mole) wasdissolved in grams of water, and to it was added 12.5 grams (0.] mole)of l,4-dicholoro-2- butene over a period of 15 to minutes whilemaintaining constant stirring. The reaction was exothermic so that thetemperature rose to about 7()C. The reaction mixture was then warmed ona steam bath at a temperature of about C. for about 1 hour, after whichthe reaction was considered complete. Titration of ionized chlorine wasused as a measure of the extent of the reaction and indicated between 98and 10071 completeness. The reaction product was a viscous materialcontaining about 50% active material.

It was found that when a significant excess of the dichlorobutene wasused, a second phase separated out of the final reaction product.Analysis indicated this second phase to contain primarily unreacteddichlorobutene.

Quite surprisingly, the compounds of this invention may be obtaineddirectly as crystalline-like solids when the reaction is carried out incertain organic solvents such isopropanol, acetone and inert halogenatedsolvents. This is illustrated as follows:

EXAMPLEZ 14.2 grams of l,4-bis-dimethylamino-2-butene were mixed with 25grams of isopropanol, and to it was added, with stirring. 12.5 grams of1.4-dichloro-2- butene over a period of about minutes (or at a ratewhich keeps the solvent gently refluxing). After the exothermic reactionsubsided, the mixture was warmed on a ateam bath to reflux temperatureand maintained at such temperature for about 1 hour. It was then cooled,to room temperature, whereby a precipitate was formed. The precipitatewas then separated out by filtration as the final product. Theprecipitate weighed 18.7 grams. This product is substantially free fromimpurities caused by side reactions or due to absorption of unreactcdstarting materials, thereby making it easier to purify for use incosmetics or cosmetic emulsions.

Solid products of the above type have the commercial advantage overaqueous solutions or dispersions because they have less bulk on a poundfor pound active ingredient basis.

EXAMPLE 3 The same reactants and procedures were used as in Example2.except that instead of the isopropanol,

grams of acetone was used. It yielded 21.4 grams of a solid product.

The same procedures may be used except that 1,4- dibromo-2-butene issubstituted for the 1,4-dichloro-2- butene, with equivalent mol ratios.The product is substantially similar in all essential characteristics.

EXAMPLE 4 142 grams of l,4'bis-dimethylamino-2-butcne were dissolved in300 ml. of 1,1 ,l-trichloroethane and to it was added slowly, withconstant stirring, 125 grams of l ,4-dichloro-2-butenc at a rate whichkept the reaction mixture at a temperature between 45 and 60C., andstirring was continued at 45 to 60C. for 1 hour after an almost-whiteprecipitate was first deposited. After cooling, the precipitatewascollected by filtration and dried in a vacuum desiccator. ltwcighed245 grams.

Various changes in relative proportions were made to determine whetherany significant variations occurred. These as illustrated as follows:

EXAMPLE 5 14.2 grams of l,4-bis-dimethylamino-2-butenc (0.1

mole) was dissolved in grams of water, and to it was added 25.0 grams of1,4-dichloro-2-butene (0.2 moles) over a period of 15-30 minutes,maintaining constant stirring. The reaction was exothermic. After 1 houranalysis for ionic chloride showed that the reaction was about 98%complete.

EXAMPLE 6 The same reactants and procedures were used as in Example 5,but the solvent was 35 grams of isopropyl alcohol instead of water.After about 1 hour, the solid polymeric product was filtered off. Itweighed about 18.7 grams. I

EXAMPLE 7 The same reactants and procedures as used in Example 5, butusing 35 grams of acetone as a solvent instead of water, gave a solidproduct which weighed 21.4 grams after filtration.

EXAMPLE 8 14.2 grams of 1,4-bis-dimethylamino-2-butene (0. 1 mole) wasdissolved in grams of water, and wit was added 37.5 grams of1,4-dichloro-2-butene over a period of 1530 minutes, maintainingconstant stirring.

The reaction was exothermic. After one hour, analysis for ionic chlorideshowed that the reaction was about 9894 complete.

EXAMPLE 9 EXAMPLE 10 The same reactants and procedures as used inExample 8, but using 45 grams of aceton'einstead of water gave a solidproduct which weighed 21.4 grams after filtration.

EXAMPLE 1 1 14.2 grams of bis-dimethylamino-Z-butene (0.1 mole) wasdissolved in 20 grams of water and to it was added 6.3 grams of1,4-dichloro-2-butene (0.05 mole) over a period of 15-30 minutes. Thereaction was exothermic. After 1 hour, analysis for ionic chloride,

showed that the reaction was about 98% complete' EXAMPLE 12 The samereactants and procedures used in Example 1 1 were used with 20 grams ofisopropyl alcohol as sol vent instead of water. After about 1 hour, the.solid f polymeric product was filtered off. It weighed. 9.4

grams.

EXAMPLE 13 The same reactants and procedures as used in Exam ple 1 1were used, except that 20 grams of acetone replaced water as solvent.After about 1 hour, the product weighed about 10.7 grams.

EXAMPLE 14 21.3 grams of 1,4-bis-dimethylamino-2-butene was (0.15 moles)dissolved in 25 grams of water, and to it was added 6.3 grams of1,4-dichloro-2-butene (0.05 moles) over a period of 15-30 minutes,maintaining constant stirring. After 1 hour, analysis for ionic ch1o--ride showed about 9871 completion.

EXAMPLE 15 The same reactants used in Example l4,but with 25 grams ofisopropyl alcohol replacing water as solvent,

produced 9.4 grams of solid polymeric product after filtration.

EXAMPLE 16 The same reactants used in Example 14, but with 25 1 grams ofacetone replacing water as solvent, produced about 10.7 grams of solidpolymeric product.

EXAMPLE '17 In order to determine the microbiocidal effectiveness of thepresent compound, the following test procedures were used:

Bactericidal Tests l. ml. volume of the product of Example 1 (here?inafter referred to as product A) was diluted in distilled water to thetest concentration, and was added asceptically to previously sterilizedcotton-stoppered 125 ml. Erlenmeyer flasks. For comparative purposes,the same test concentration was prepared using another knownmicrobiocidal polymeric quaternary ammonium compound, namely a productproduced by the reaction of bis(2-chlorocthyl) ether and tetramethylethylenediamine (hereinafter referred to as Product B").

2. One set of test flasks were each inoculated with 0.5 ml. of a 1/10nutrient broth dilution of a 24-hour nutrient broth culture ofAerobactcr aerogenes and another set of test flasks were each inoculatedwith 0.5 ml. of a one-tenth nutrient broth dilution of a 24-hour nutrient broth culture of Pseudomonas aeruginosa.

3. At 30 and 60, minutes following inoculation, a 1 ml. aliquot of eachproduct was removed rrom each flask and added to 9 ml. of sterileazolectin/Tween 80" neutralizer from which additional fold serialdilutions were prepared in the sterile neutralizer solution.

4. Agar plate counts were prepared from 10 and 10 dilutions.

5. A control of sterile distilled water was similarly inoculated andaliquots were made at the same intervals and plates at 10*, 10", and 10dilutions.

6. A comparison of the surviving organisms for various concentrations oftest materials, at the different time periods was made. The results wereas follows:

Table l AGAINST PSI-IUDUMONAS AEROGINOSA Cone. No. of Bacteria SurvivingAfter Sample in ppm. 30 min. 60 min.

Product A 75 29,600 18,500

Product B" 150 26.000 6,800

-Untretlted 8,500,000 12,500,000

(Control) Table 2 AGAlNST AEROBACI'IJR AERUGl-INLZS Cone. No. ofBacteria Surviving After Sample in ppm. 30 min. 60 min.

Product A" 20 5,600 4,300 50 3,000 1 ,1 100 "Product 13" 100 30,00030,000

Untreated (Control) 10,500,000 1 1,000,000

Table 3 The following 'l'ahlc comprises a comparison of Product A" and"Product B" at identical concentrations:

AGAINST AI-[ROIMCI'l-JR AEROGENl-IS' Algaestatie Tests 1. 24 ml. volumesof Product A and Product B were prepared in sterile Erlenmeyer flasks atvarious test concentrations.

2. 1 ml. of 5-7 days Allen's liquid medium growth of Chlorellapyrenoidosa (Wise. strain) was added to each flask (Allens liquid mediumis a standard test composition comprising mg. NH,C1, 1000 mg. NaNo 250mg. K HPO 3 mg. FcCl 513 mg. MgSO 50 mg. CaCl and 1000 mil. distilledwater).

3. The inoculated flasks. plus untreated inoculated control flasks, wereincubated at room temperature (about 25C.) under continuous artificialillumination.

4. Following 5 to 7 days incubation, observation was made formacroscopic growth to determine the minimum inhibitory level for eachtest material.

The results were as follows:

Table 4 Sample Minimum effective concentration in ppm.

Product A" 1.0 "Product 13" 1.5

A graduated blender cylinder is rinsed with distilled water. ml, ofaqueous test solution is added downthe walls of the blender so as tocause no foam. the blender is turned to high speed for exactly 5seconds, and upon turning the blades off, timing is started with a stopwatch, and at the same time the foam height read in mm. from the 100 ml.mark. The foam half-life is defined as the time it takes for liquid todrain out of the foam and reach the 50 ml. mark.

A further test was made using the Cylinder Shake Test procedure which isas follows:

CYLINDER SHAKE TEST I ml. of test solution is gently poured down thewalls of a 250 ml. graduated cylinder that has a glass stopper. Thecylinder is stoppered and inverted times in 15 seconds, finally restingit in an upright position. The foam height is read in cc. from the baseof the foam.

Table 6 Foam Height in cc. Sample ppm. Initial l min. 5 min.

B'I'C 77(1" 50 45 34 Product A" St) (I (l "BTC 2l25" 5U 50 (i 4 Anothertest used was .the standard Ross-Miles Test using the procedure reportedin "ASTM Standards, Designation 1175-53, Part X, 1958, page 878," whichis the ASTM test for foaming properties of surface active material. Theresults were as follows;

Table 7 Foam Height in cc. Sample ppm. Initial I min. 5 min.

BTC 776' 50 30 20 Product A" 50 0 t) I) BTC 2l25" 5O 35 I5 I() The aboveresults clearly show not only that the product of this invention ishighly biocidal but that it is non-foaming, whcreasother quaternaryammonium bi ocides cause a relatively large amount of foaming in aqueouscomposition.

The following examples illustrate various cosmetic compositions usingthe product of the present invention:

Example I8 Components 71 by Wt. I by by Wt. "/r by Wt.

Mineral oil (65/75 VisC.) 35.0 35.0 35.0 35.0

Lanolin (Cosmetic Grade) l.() 1.0 1.0 l.()

Celyl alcohol I.() l.() l.() 1.!)

'IWEEN 8t)" (Atlas Powder Co.) (non-ionic "SPAN Rt) (Atlas Powder Co.)(non-ionic emulsifier) "Product A Water (Distilled) 55.0

In the case of the first formulation, without Product A A, the mineraloil, lanolin, cetyl alcohol, Tween 80, and Span 80 were combined andheated to about (157()C. The water was heated to about 7()C. and addedslowly to the hot non-aqucousphase while stirring the mixture until itemulsified completely. The emulsion was cooled to room temperatureusingcon-. tinued agitation.

In each formulation when Product A was incorporated. the mineral oil,lanolin, cetyl alcohol,Twee n.8(), and Span were combined and heated toabout 657()C. The water and Product A were combined and heated to about6570C. Then the hot aqueous solution was added slowly to the hotnon-aqueous phase while stirring, and agitation was maintained untilemulsification was effected. Then the emulsion was cooled with continuedstirring to room temperature. The resultant product was an oil-in-wateremulsion.

These compositions are utilizable as hand creams and baby lotions.

These compositions were tested in thefollowing manner:

50 gm. samples from each composition were aseptieally transferred tosterile 8 02. wide mouth jars. Two replicate jars were prepared ineveryinstance, includ; ing an untreated control. Each jar was inoculatedwith 2.5 ml. of a one-ten sterile nutrient heated dilution of pooled 24hour broth cultures of Staphylococcus aureus. Pseudomonas aeruginosa,Escherichia coli, Enterobacteraerogenes, proteus species and Bacillusspe cies. In this manner a bacterial challenge load of l-l OX 1 Obacteria/nil. ofjar content was obtained. All. the inoculated jars werestored at 2527C. At weekly intervals following inoculation, 1 ml.aliquots of jar content were removed from each jar and tenfold serialdilutions were prepared therefrom in stcrile A zalectin/- Tween 80neutralizer solution which wereplated into TGE a jar. In this manner thenumber of surviving viable bacteria in each jar was determined. In thoseinstances where no viable surviving bacteria lO bac.teria) were observedat four weeks following inoculation,

the jar contents were reinoculated exactly as previously and IOXIObacteria/ml. The. variation around the mean of the inoculumconcentration is of little importance when a reduction to less thanlO/ml. ofviable l bacteria is observed.

Table 8 INOCULATION at 6 X It) organisms/nth ol'jar content for each ofthe four formulations of Example 18.

From a statistical point of view, there is no significant differencebetween an initial inoculum load of IX I 0 Week Count Count Count CountI (19 X H)" l5.()(l() II) 10' 2 71 X [0" 74,000 H) l() 3 54 X It) 1.400l(). [0 4 XI II) II) 10 In order to double'check the validity of thistest showing less than 10 organisms/ml. after four weeks,

the samples were rcinoculat cd and the weekly counts Table 10 afterreinoculation were:

INOCULATION at 3.8X10 organisms/ml. of jar content for each o1- the fourformulations o1- Example 20:

Week Count Count Count Count 5 Count Count Count Count eek 5 10K X10" 1010 10 6 169 X 10" 10 10 10 I [8x100 ISXIOIF RXXIUH 7 180x10" 10 10 10 223x1 :lxloli IZXIU ()IZXHW 8 209 X 10' 10 10 10 3 87x10 7 84x10"sfixloli 4 l()(t l0' 50x10" 70x10" 80x10" 10 5 109x10" 114x10" 50x10"20x10" UZXIU 7'JXI1)" 45Xl0" 36 l0' The followmg example were preparedin the same 4X10 89x10" 67x10 750x10" manner as Example 18, butsubstnutmg other well- 8 fi mzxmfi xlxm" known, highly active biocidalquaternary ammonium compounds for Product A. They were then similarlyevaluated.

Ex'tm 1e 19 p Example 21 I" F I/ I" Componuns h W1. 1 h Wt. by Wt. h Wt.Comlmmms (/1 by wt. by wt WL Mimml *1" Mineral 011 55.0 55.0 55.0 55.0105/75 VISC.) 35.0 35.0 35.0 55.0 (65/75 visa) Lanolin Lanolin (CosmeticGrade) 1.0 1.0 (Cosmetic Cetyl Alcohol 1.0 1.0 1.0 1 0 Grade) 1.0 1.01.0 1.0 TWEEN 150" 5.4 .1 5.4 Cetyl alcohol 1.0 1.0 1.0 1.0 SPAN 110 2.02.0 2.0 2.0 E 80' 5.4 .4 5.4 5.4 BTC snr SPAN 80 2.6 .0 2.6 2.6 (On\'x(711001.01) 0 0.1 0.2 04 HYAMINE 1633 Water (507') (131511110111 55.054.0 54.1: 54.0

Table 9 lNOCULATlON at 4.7 X 1()orgnnisn1s/ml. o1 jar content for eachof the lour formulations of Example 19.

. Table 1 1 Count Count Count Count cck INOCULATION at 3.1"1 l0organisms/ml. ot' jar content for each i 40 of the four formulations ofExample 21: 1 10x10- 10x10" 10x10" 4x10" 3 98x10" 13x10" 1 1X10" 5X10"Count Count Count Count 1 07x10" 40x10 24x10 10x10" COR 4 142x10" lt)284x10" 01x10" 5 167Xl0" l19 l0 X4Xl0" (17 l0 l ZZXIU 19X 10 l7 l0"' l5l0 6 180x10" l 14 10 32x11)" 44x11)" 2 P.4Xl0 21x11)" 19 l0 l -l l0 7140x10" 95x10 82x10" 70x10" 3 80x10" 71x10" 94x10" 111x10" 8 4 0" 2 1 054 4 94x10 80x10 72Xl0 92X10" 5 106 l0 74 10" 67 l0 x10" 6 l loXlt)91x10 84x10 X10 7 '-)Z l() 74 l0' 4ZX10 ZXXH)" 8 94X10" 82x10" 56 10'43Xl0" 50 Example 20 Components "/1 by Wt. 71 hy Wt. 71 by Wt. by Wt.

Mineral oil gs (65/75 \-1se.) 35.0 35.0 35.0 35.0 Example 22 Lanolin(Cosmetic (irade) 1.0 1.0 1.0 1.0 Components "/1 by Wt. '/r by Wt. byWt. 71 by Wt.

Cetyl alcohol 1.0 1.0 1.0 1.0 Mineral oil 0 (65/75 Vise.) 35.0 35.0 35.035.0 TWEEN 110" 5.4 5.4 5.4 0 5.4 Lwmlin (Cosmetic (irade) 1.0 1.0 1.01.0

. Z. 2. 2. 2X 51 AN 6 Cetyl 111001101 1.0 1.0 1.0 1.0 TWEEN 5.4 5.4 5.45.4 i 3135M "SPAN 2.0 2.0 2.0 2.0 HYAMINE 23110" (Onyx henLC o.) 0 0.10.2 0.4 1

(Robin & Haas) 0 0.1 0.2 0.4 Water Water (Distilled) 5540 54.) 54.1 5(Distilled) 55.0 54.9 54.8 54.6

Table 12 INOCULATION at 4.l'l l() organisms/ml. of jar content for eachof the four fornnilations of Example 22:

Although oil-in-water emulsions have been described above, it is withinthe scope of the present invention to use water-in-oil emulsions for thesame purposes.

The invention claimed is:

l. A method of controlling the proliferation of deleteriousmicroorganisms selected from the group consisting of bacteria and algaein an aqueous system, which comprises applying to said microorganisms ahacteriacidally or algaecidally effective amount of a condensationproduct formed'by mixing l,4-bisdimethylamino-Z-butene dissolved in asolvent with 1,4- dihalo-Z-butene at room temperature whereby anexothermic reaction is obtained causing the temperature of the mixtureto rise, then maintaining the mixture at no higher than refluxtemperature until the reaction is LII complete, wherein these reactantsarepresent ina molar proportion of between about 1:3 and about 321relative to each other.

2. The method of claim 1 wherein the dihalo is dichloro.

3. The method of claim 1 wherein the dihalo. is dibromo.

4. The method of claim 1 wherein the aqueousmedia is recirculated water.

5. An aqueous composition containing, as a biocidal agent, thecondensation product formed by mixing] ,4- a

bis-dimethylamino-Z-butene dissolved in a solvent withl,4-dihalo-2-butene at room temperature whereby an .exothcrmicreactionis obtained causing the temperature of the mixture to rise, thenmaintaining the mixture at no higher than reflux temperature until thereaction is complete, wherein these reactants are in a molar proportionof between about about 1:3 and about 3:]

relative to each other, said agent being present in a bacteriacidally oralgaecidally effective amount.

6. The composition of claim 5 wherein said aqueous media comprisesrecirculating water.

1. A METHOD OF CONTROLLING THE PROLIFERATION OF DELETERIOUSMICROORGANISMS SELECTED FROM THE GROUP CONSISTING OF BACTERIA AND ALGAEIN AN AQUEOUS SYSTEM, WHICH COMPRISES APPLYING TO SAID MICROOGANISMS ABACTERIACIDALLY OR ALAECIDALLY EFFECTIVE AMOUNT OF A CONDENSATIONPRODUCT FORMED BY MIXING 1,4BISIDIMETHYLAMINO-2-BUTENE DISSOLVED IN ASOLVENT WITH 1,4DIHALO-2-BUTENE AT ROOM TEMPERATURE WHEREBY ANEXOTHERMIC REACTION IS OBTAINED CAUSING THE TEMPERATURE OF THE MIXTURETO RISE, THEN MAINTAINING THE MIXTURE AT NO HIGHER THAN REFLUXTEMPERATURE UNTIL THE REACTION COMPLETE,
 2. The method of claim 1wherein the dihalo is dichloro.
 3. The method of claim 1 wherein thedihalo is dibromo.
 4. The method of claim 1 wherein the aqueous media isrecirculated water.
 5. An aqueous composition containing, as a biocidalagent, the condensation product formed by mixing1,4-bis-dimethylamino-2-butene dissolved in a solvent with1,4-dihalo-2-butene at room temperature whereby an exothermic reactionis Obtained causing the temperature of the mixture to rise, thenmaintaining the mixture at no higher than reflux temperature until thereaction is complete, wherein these reactants are in a molar proportionof between about about 1:3 and about 3:1 relative to each other, saidagent being present in a bacteriacidally or algaecidally effectiveamount.
 6. The composition of claim 5 wherein said aqueous mediacomprises recirculating water.
 7. The composition of claim 5 whereinsaid composition is an aqueous emulsion containing non-ionicemulsifiers.
 8. The composition of claim 5 wherein said composition is ahand cream or baby lotion.